玻璃化转变的热力学理论错在哪里?

What's Wrong in the Thermodynamic Theory of Glass Transition?

现行国内高分子物理学教科书上都介绍玻璃化转变的热力学理论,其把玻璃化转变描述成为一个二级相转变。但是现在人们已经普遍接受玻璃化转变的本质是一个动力学过程的观点。我们通过讨论玻璃化转变热力学理论的来历,试图弄清这一理论到底错在哪里。首先,该理论所基于的Kauzmann佯谬可能不是一个真正的佯谬;其次,半柔顺链高分子溶液的经典格子统计理论结果中所谓的熵灾难可能是出于对构型熵的错误理解所致。因此,把以上二者联系起来构成玻璃化转变热力学理论的基本假定就从根本上来说是不可靠的。

Current textbooks of polymer physics commonly introduce the thermodynamic theory of glass transition, which describes the glass transition as a second-order phase transition. However, people have generally accepted the point of view that the nature of glass transition is a kinetic process. We discussed the origin of the thermodynamic theory of glass transition and tried to figure out the false assumptions employed in this theory. First, we pointed out that the famous Kauzmann paradox may not be a real paradox. Second, we told the reader that the so-called entropy catastrophe in the result of Flory＇s lattice statistics of semiflexible polymer solutions may rest on a misinterpretation of the configurational entropy, and the latter actually means free energy. Therefore, combining the above paradox with the above catastrophe into the basic assumptions of the thermodynamic theory of glass transition may lead to an illusive result.